KR101111040B1 - Polyester film for molding - Google Patents

Abstract

[PROBLEMS] The present invention is excellent in moldability, transparency, solvent resistance, and heat resistance at low temperature and low pressure, and also prevents blocking or film tearing when unwinding a long film wound in a roll shape. It is an object of the present invention to provide a molding polyester film suitable as a name plate or building material member for home appliances, automobiles, and the like, which does not occur and has a small environmental load.

[Solution] The molding polyester film of the present invention for solving the above problems is a molding polyester film which is a biaxially oriented polyester film containing a copolyester, and (1) the longitudinal direction and the width direction of the film. The 100% elongation at 100% of the stress at 25 ° C is in the range of 1 to 100 MPa at 25 ° C and 100 ° C, and (2) the heat shrinkage in the longitudinal direction and the width direction at 150 ° C of the film is 0.01 to 5.0. %, (3) haze of 0.1-3.0%, (4) Surface roughness Ra of the film of at least one surface is 0.005-0.030 micrometer, (5) Surface orientation is 0.095 or less, It is characterized by the above-mentioned.

Description

Polyester film for molding {Polyester film for molding}

The present invention is excellent in moldability, transparency, solvent resistance, and heat resistance at low temperature and low pressure, and no blocking or tearing of film occurs when unwinding a long film wound in a roll shape. The present invention also relates to a polyester film for molding suitable as a box or a member of various portable devices, a name plate member of a home appliance or an automobile, or a member for building materials having a small environmental load. Moreover, it is related with the polyester film for shaping | molding which is excellent also in light resistance suitable for the use (member for exterior or building materials of automobiles) used outdoors.

Furthermore, it is related with the film for shaping | molding which provided the hard-coat layer which was excellent in moldability and excellent in scratch resistance.

Conventionally, as a sheet for shaping | molding, polyvinyl chloride film is typically used suitably from a viewpoint of workability. On the other hand, the film has problems such as generation of toxic gas when the film is burned due to fire, bleeding out of plasticizer, etc., and according to the recent demand for environmental resistance, new materials having a small environmental load have been demanded. .

In order to satisfy the above requirements, an unstretched sheet made of polyester, polycarbonate, and acrylic resin has been used in a wide range of fields as a non-chlorine material. In particular, an unstretched sheet made of a polyester resin is attracting attention due to its good mechanical properties and transparency and excellent economic efficiency. For example, an unstretched polyester-based sheet comprising substantially amorphous polyester-based resin in which about 30 mol% of the ethylene glycol component in polyethylene terephthalate is substituted with 1,4-cyclohexanedimethanol Is disclosed (for example, refer patent documents 1-5).

Patent Document 1: Japanese Patent Application Laid-Open No. 9-156267

Patent Document 2: Japanese Patent Application Laid-Open No. 2001-71669

Patent Document 3: Japanese Patent Application Laid-Open No. 2001-80251

Patent Document 4: Japanese Patent Application Laid-Open No. 2001-129951

Patent Document 5: Japanese Patent Application Laid-Open No. 2002-249652

Although the above unstretched polyester sheet satisfies the market demand in terms of moldability and laminate aptitude, the unstretched sheet does not have sufficient heat resistance and solvent resistance because it is an unstretched sheet, and does not reach the high demand of the market. have.

As a method of solving the said subject, the method of using a biaxially stretched polyethylene terephthalate film is disclosed (for example, refer patent document 6-9).

Patent Document 6: Japanese Patent Application Laid-Open No. 9-187903

Patent Document 7: Japanese Patent Application Laid-Open No. 10-296937

Patent Document 8: Japanese Patent Application Laid-Open No. 11-10816

Patent Document 9: Japanese Patent Application Laid-Open No. 11-268215

However, the above method improves heat resistance and solvent resistance, but has insufficient moldability and does not satisfy market demand in terms of overall quality balance.

As a method of solving the said subject, the method of specifying the stress at 100% elongation of a film is disclosed (for example, refer patent document 10, 11).

Patent Document 10: Japanese Patent Application Laid-Open No. 2-204020

Patent Document 11: Japanese Patent Application Laid-Open No. 2001-347565

This method has improved formability compared to the above method, but has not reached a level that can sufficiently meet the high demands of the market regarding formability. In particular, problems remain in the formability which can be suitable for lowering the molding temperature and the finishability of the obtained molded article.

The present inventors have studied about the above-mentioned problem solving, and have already proposed a method of improving the above problem by specifying the copolyester resin of a specific composition as a raw material and specifying the stress at 100% elongation of the film. For example, refer patent document 12).

Patent Document 12: Japanese Patent Application Laid-Open No. 2004-075713

By this method, in the mold forming method having a high molding pressure at the time of molding, the moldability suitable for lowering the molding temperature, which satisfies the market demand, and the finish of the obtained molded article can be greatly improved. However, in the case of a molding method having a low molding pressure at the time of molding such as a pressure molding method or a vacuum molding method which is strongly demanded in the market in recent years, it is desired to further improve the finish of molded articles.

In addition, the polyester film for molding which can be applied to the compression molding method or the vacuum molding method, which is a molding method having a low molding pressure at the time of molding, is a biaxially stretched polyester film containing a copolyester, and the film is 25 ° C. and 100 ° C. The present inventors proposed a molding polyester film having a specific range of a stress at 100% elongation in ° C, a storage modulus (E ') at 100 ° C and 180 ° C, and a thermal strain at 175 ° C. See, for example, Patent Document 13). However, it was found that blocking and tearing are likely to occur when the film is continuously produced and wound up in a roll, and then the film is unwound and post-processed. For this reason, when post-processing, such as depositing or sputtering a metal and a metal oxide on a film, or performing printing, it is desired to further improve stability of productivity and quality.

Patent Document 13: Japanese Patent Application Laid-Open No. 2005-290354

DISCLOSURE OF INVENTION

Problems to be Solved by the Invention

SUMMARY OF THE INVENTION An object of the present invention is to solve the above-mentioned conventional problems, which is excellent in formability, transparency, solvent resistance, and heat resistance at low temperature and low pressure, and also prevents blocking or tearing of the film when unwinding a long film wound into a roll. The present invention provides a molding polyester film suitable as a box or a member of various portable devices, a name plate member of a home appliance or an automobile, or a member for building materials, which does not occur and has a small environmental load.

Means to solve the problem

The polyester film for shaping | molding of this invention which can solve the said subject becomes the following structures.

1st invention in this invention is a polyester film for shaping | molding which becomes a biaxially-oriented polyester film containing a copolyester, (1) 100% elongation stress in the longitudinal direction and the width direction of a film are all 1 to 100 MPa at 25 ° C and 100 to 100 ° C, (2) Heat shrinkage in the longitudinal and width directions at 150 ° C of film is 0.01 to 5.0%, and (3) haze is 0.1 to 3.0% And (4) Surface roughness Ra of at least one surface is 0.005-0.030 micrometer, and (5) surface orientation is 0.095 or less, The polyester film for shaping | molding characterized by the above-mentioned.

2nd invention is a polyester film for shaping | molding of 1st invention characterized by the biaxially-oriented polyester film containing a ultraviolet absorber, and the light transmittance in wavelength 370nm being 50% or less.

In a third aspect of the present invention, the copolymerized polyester comprises (a) an aromatic dicarboxylic acid component, a glycol component comprising ethylene glycol and branched aliphatic glycols or alicyclic glycols, or (b) terephthalic acid and iso It is a co-polyester comprised from the aromatic dicarboxylic acid component containing a phthalic acid, and the glycol component containing ethylene glycol, It is a polyester film for shaping | molding in 1st or 2nd invention characterized by the above-mentioned.

In the fourth aspect of the present invention, the polyester constituting the biaxially oriented polyester film further includes 1,3-propanediol units or 1,4-butanediol units as glycol components. It is a film.

5th invention is a polyester film for shaping | molding in any one of 1st-4 invention characterized by the melting | fusing point of a biaxially-oriented polyester film 200-245 degreeC.

6th invention is a polyester film for shaping | molding which uses a biaxially-oriented polyester film as a base film, and laminates the surface layer which is 0.01-5 micrometers in thickness on one or both surfaces of this base film, The said base film is substantially It is a polyester film for shaping | molding in any one of the 1st-5th invention characterized by including particle | grains only in a surface layer, without containing particle | grains.

7th invention is a polyester film for shaping | molding as described in 6th invention whose surface layer mainly consists of adhesive modified resin and particle | grains.

8th invention is the shaping | molding polyester film which provided the hard-coat layer in at least one surface of the shaping | molding polyester film of any one of said 1st-7th invention.

A ninth invention is a polyester molded article obtained by molding the polyester film for molding according to any one of the first to eighth methods by any one of vacuum molding, pressure molding and mold molding.

A tenth invention is a polyester molded article provided with a hard coat layer on at least one side of the polyester molded article of the ninth invention.

Effects of the Invention

The polyester film for molding of the present invention can be applied to a wide range of molding methods because of its excellent moldability at the time of heat molding under low temperature or low pressure, and also when used under normal temperature atmosphere as a molded article, elasticity and form stability (heat shrinkage). Characteristics, thickness nonuniformity), and solvent resistance, heat resistance, and environmental load are small. Moreover, when unwinding the long film wound up in roll shape at the time of post-processing, since blocking and tearing hardly occur, productivity is excellent. Moreover, since smoothness and transparency are highly excellent, the designability at the time of providing a vapor deposition layer, a sputtering layer, or a printing layer at the time of post-processing is excellent. For this reason, it is suitable as the box body of various portable devices, its member, the nameplate member of a household appliance or an automobile, or a member for building materials.

Moreover, by containing a ultraviolet absorber in a film and reducing the transmittance | permeability of an ultraviolet region, light resistance can be provided and it is especially suitable as a shaping | molding material for the use (member for exterior or building materials of automobiles) used outdoors.

Carrying out the invention  Best form for

First, the technical meaning of the physical property prescribed | regulated by the moldable polyester film of this invention is demonstrated. Next, the method for manufacturing the moldable polyester film of this invention is demonstrated.

(Technical Meaning and Significance of Physical Properties Described in the Present Invention)

In the present invention, the stress at 100% elongation (F100) is a measure closely related to the moldability of the film. As a reason why F100 is closely related to the moldability of the film, for example, when forming a biaxially oriented polyester film using a vacuum molding method, the film may be locally stretched to 100% or more near the corner of the mold. In a film with a high F100, such a locally stretched portion may generate a very high stress in part, and the film may break due to this stress concentration, thereby degrading the moldability. On the other hand, in the film where F100 is too small, the moldability becomes good, but only a very weak tension is generated in the uniformly elongated portion such as the flat portion of the mold. As a result, the uniform elongation of the film in this portion is It may be that it is not obtained.

In the present invention, 100% elongation stress (F100 ₁₀₀ ) at 100 ° C is used as physical properties related to moldability corresponding to the temperature at the time of molding. In addition, when molding using a mold having irregularities or a pan, it is a physical property related to the moldability when the film before molding is molded by lightly harvesting them in their mold beforehand. 100% elongation at stress (F100 ₂₅ ) is used.

As for the polyester film for shaping | molding in this invention, all the stress (F10025) at 100% elongation at ₂₅ degreeC in the longitudinal direction and the width direction of a film are 30-300 Mpa.

F100 ₂₅ in the longitudinal direction and the width direction of a film is 40-300 Mpa, A minimum value is 50 Mpa, More preferably, it is 60 Mpa. The upper limit is preferably 250 MPa, more preferably 200 MPa, still more preferably 180 MPa. F100, if ₂₅ is less than 40 ㎫, when pulling out the film on the roll volume invoke, the workability becomes poor since the film is stretched or torn. On the other hand, if the F100 ₂₅ exceeds 300 ㎫, the moldability becomes poor. In particular, in the case of molding using a mold having unevenness or a pan, the film before molding may be lightly harvested into their molds beforehand to be molded. In such a case, the form of the film becomes difficult to be produced, and the designability of the finished product may be poor.

Moreover, it is important that the polyester film for shaping | molding in this invention is 100-100 Mpa of 100% elongation stress at ₁₀₀ degreeC in ₁₀₀ degreeC in the longitudinal direction and the width direction of a film.

90 MPa is preferable, as for the upper limit of F100 ₁₀₀ in the longitudinal direction and the width direction of a film, 80 MPa is more preferable, and 70 MPa is especially preferable. On the other hand, the lower limit of F100 ₁₀₀ is preferably 5 MPa, more preferably 10 MPa, and particularly preferably 20 MPa from the viewpoint of elasticity and form stability when using a molded article.

In the film of this invention, the thermal contraction rate in the longitudinal direction and the width direction in 150 degreeC is 0.01 to 5.0%. 0.1% is preferable and, as for the minimum of the thermal contraction rate in 150 degreeC, More preferably, it is 0.5%. On the other hand, as for the upper limit of the thermal contraction rate in 150 degreeC, 4.5% is preferable, More preferably, it is 4.1%, More preferably, it is 3.2%. Even when the biaxially stretched polyester film for molding having a heat shrinkage ratio of the film in the longitudinal direction and the width direction at 150 ° C. is less than 0.01% is produced, no significant difference is seen in the practical effect, and the productivity is very low. There is no necessity to make the heat shrinkage less than 0.01%. On the other hand, when the thermal contraction rate of the film in the longitudinal direction and the width direction at 150 ° C exceeds 5.0%, the film tends to deform in a post-treatment step in which heat such as vapor deposition, sputtering or printing is applied, and the film after post-processing The appearance and design of the product becomes poor.

In addition, in this invention, the haze of a film is 0.1 to 3.0%. The lower limit of the haze is preferably 0.3%, more preferably 0.5%. On the other hand, 2.5% of the upper limit of haze is preferable, More preferably, it is 2.0%. Since the film whose haze is less than 0.1% has bad activity, it is difficult to produce on industrial scale by normal productivity. On the other hand, when the haze of a film exceeds 3.0%, when a vapor deposition, a sputtering surface, or a printing surface of metal, etc. is seen from the back surface of a film, a metal or a printing surface will look blackish, and designability will become inadequate. . In addition, it is difficult to obtain a film having a haze of 2.0% or less by a method of forming irregularities on the film surface by containing particles in the film, which is generally performed for improvement of handling properties in the film.

In this invention, the surface roughness Ra of the film of at least one surface is 0.005-0.030 micrometer. The lower limit of Ra is preferably 0.006 µm, more preferably 0.007 µm. On the other hand, as for the upper limit of Ra, 0.025 micrometer is preferable, More preferably, it is 0.015 micrometer. As Ra of the film of at least one surface becomes small, it becomes difficult to wind up a film, and also the frequency of blocking and tearing of a film increases when unwinding the film wound up once in roll shape. Moreover, when Ra exceeds 0.03 micrometer, a protrusion will become a fault in post-processing processes, such as vapor deposition, sputtering, or printing, and designability will fall.

In the present invention, the plane orientation degree ΔP of the film is also a physical property related to formability. As the plane orientation degree is higher, molecular chains are arranged in the plane direction, and the moldability is lowered. In this invention, the plane orientation of a film is 0.095 or less. As for the upper limit of surface orientation, 0.090 is preferable. In addition, the smaller the surface orientation, the better the moldability, but the strength of the film decreases, and the flatness such as thickness unevenness tends to deteriorate. Therefore, the lower limit of the plane orientation is preferably 0.001, more preferably 0.01, and particularly preferably 0.04.

(Idea of the present invention)

This application is an improvement of patent document 12 described in the prior art.

The polyester film obtained by using the copolyester containing 5-50 mol% of copolymerization components as a raw material like this invention has a slow crystallization rate and low crystallinity compared with a polyethylene terephthalate film etc. In addition, in order to reduce the surface orientation and thermal contraction rate of 150 ° C., when the method of heat treatment at a higher temperature than that described in Patent Document 12 is used, the heat treatment is rapidly performed at the high temperature after the completion of the stretching, so that the crystallinity in the heat treatment zone is increased. Mobility of the molecules constituting this low material is increased. Therefore, since the surface protrusion formed when the particles (particles in the biaxially oriented film or particles in the coating layer) are raised in the stretching step, is buried again in the heat treatment zone, sufficient surface roughness cannot be obtained. For this reason, there is a problem that the haze deteriorates when the amount of the particles added is increased more than necessary in order to wind the film cleanly and to suppress blocking and tearing when unwinding the film wound into a roll.

In the present invention, the above problems are solved by using a suitable method of controlling the heat treatment temperature TS1 of the first stage and the heat treatment temperature TS2 of the second stage to a specific range by setting the heat treatment zone to two stages (or more). This mechanism is considered as follows.

In the heat treatment zone of the first stage, before the particles are buried in the film, even if the crystallization of the film is promoted to some extent, and the temperature is sufficiently increased in the heat treatment zone of the second stage, the mobility of the molecules is sufficiently lowered. With the surface projections formed, crystallinity is further promoted, and a film with low thermal shrinkage is obtained. Moreover, it becomes unnecessary to contain a particle more than necessary from a transparency point of view.

(Proper manufacturing method of film)

The molding polyester film of this invention uses co-polyester as a raw material. The copolyester includes (a) an aromatic dicarboxylic acid component, a copolymerized polyester composed of ethylene glycol and a glycol component containing branched aliphatic glycols or alicyclic glycols, or (b) terephthalic acid and isophthalic acid. Copolyesters composed of an aromatic dicarboxylic acid component and a glycol component containing ethylene glycol are suitable. Moreover, it is preferable that the polyester which comprises a biaxially-oriented polyester film contains 1, 3- propanediol unit or 1, 4- butanediol unit further as a glycol component from a viewpoint of further improving moldability.

In the present invention, as the film raw material, any of co-polyester alone, a blend of one or more types of homopolyester or copolyester, or a combination of homopolyester and copolyester may be used. Among these, the blend method is suitable from the viewpoint of suppressing the fall of the melting point.

As said copolyester, when using the copolyester comprised from the aromatic dicarboxylic acid component, the ethylene glycol, and the glycol component containing branched aliphatic glycol or alicyclic glycol, as an aromatic dicarboxylic acid component, Terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid or ester forming derivatives thereof are suitable, and the amount of terephthalic acid and / or naphthalenedicarboxylic acid component relative to the total dicarboxylic acid component is 70 mol% or more, preferably 85 mol. At least%, particularly preferably at least 95 mol%, particularly preferably 100 mol%.

As the branched aliphatic glycol, for example, neopentyl glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol and the like are exemplified. As alicyclic glycol, 1, 4- cyclohexane dimethanol, tricyclodecane dimethylol, etc. are illustrated.

Among these, neopentyl glycol and 1, 4- cyclohexane dimethanol are especially preferable. Moreover, in this invention, it is a more preferable embodiment to make 1, 3- propanediol and 1, 4- butanediol as a copolymerization component in addition to said glycol component. The use of these glycols as copolymerization components is suitable for imparting the above characteristics, and is also excellent in transparency and heat resistance, and is also preferable in terms of improving adhesion to the adhesive modifying layer.

In addition, when using the copolymer polyester which consists of the aromatic dicarboxylic acid component containing terephthalic acid and isophthalic acid, and the glycol component containing ethylene glycol as said copolyester, the quantity of ethylene glycol is the total glycol component. At least 70 mol%, preferably at least 85 mol%, particularly preferably at least 95 mol%, particularly preferably 100 mol%. As glycol components other than ethylene glycol, said branched aliphatic glycol, alicyclic glycol, or diethylene glycol is suitable.

As a catalyst used when producing the copolyester, for example, an alkaline earth metal compound, a manganese compound, a cobalt compound, an aluminum compound, an antimony compound, a titanium compound, a titanium / silicon composite oxide, a germanium compound, or the like can be used. Among these, titanium compounds, antimony compounds, germanium compounds, and aluminum compounds are preferable in terms of catalytic activity.

When manufacturing the said copolyester, it is preferable to add a phosphorus compound as a heat stabilizer. As said phosphorus compound, phosphoric acid, phosphorous acid, etc. are preferable, for example.

The copolyester preferably has an intrinsic viscosity of 0.50 dl / g or more, more preferably 0.55 dl / g or more, particularly preferably 0.60 dl / g or more in view of moldability, adhesiveness and film forming stability. If the intrinsic viscosity is less than 0.50 dl / g, the moldability tends to be lowered. In addition, when a filter for removing foreign matters is provided in the melt line, it is preferable to set the upper limit of the intrinsic viscosity to 1.0 dl / g in view of the discharge stability at the time of extrusion of the molten resin.

In the present invention, by using one or more types of homopolyester or copolyester as a film raw material and blending them to form a film, transparency and high melting point (heat resistance) can be realized while maintaining the same flexibility as in the case of using only copolyester. Can be. In addition, in the case where only a high melting point homopolyester (for example, polyethylene terephthalate) is used, it is possible to realize a melting point (heat resistance) without problems of flexibility and practicality while maintaining high transparency.

Furthermore, at least 1 type or more of the said copolyester and homopolyesters (for example, polytetramethylene terephthalate and polybutylene terephthalate) other than a polyethylene terephthalate are blended, and the polyester film for shaping | molding of this invention is carried out. It is more preferable also to use as a raw material from a moldability viewpoint.

It is preferable that melting | fusing point of the said polyester film is 200-245 degreeC from a heat resistance and a moldability viewpoint. By controlling the type and composition of the polymer to be used and the film forming conditions within the range of the melting point, it is possible to balance formability and finish, and to produce high quality molded articles economically. Here, melting | fusing point is the endothermic peak temperature at the time of melting detected at the time of 1st temperature rise of what is called differential scanning calorimetry (DSC). This melting point was determined by using a differential scanning calorimetry device (DSC 3100S, manufactured by Mac Science, Inc.) at a heating rate of 20 ° C./min. The lower limit of the melting point is more preferably 210 ° C, particularly preferably 230 ° C. If melting | fusing point is less than 200 degreeC, there exists a tendency for heat resistance to deteriorate. For this reason, when exposed to high temperature at the time of shaping | molding or the use of a molded article, it may become a problem.

Moreover, it is preferable that the light transmittance in wavelength 370nm of the polyester film for shaping | molding of this invention is 50% or less, More preferably, it is 40% or less, Especially preferably, it is 30% or less. By controlling the light transmittance at a wavelength of 370 nm of the polyester film for molding to 50% or less, the light resistance of the printing layer is particularly improved when the film is printed.

As a method of controlling the light transmittance at said wavelength 370nm to 50% or less, the method of mix | blending a ultraviolet absorber with any one of the structural layers of the polyester film for shaping | molding is used. The ultraviolet absorbent may be either inorganic or organic as long as it can provide the above characteristics. As an organic type ultraviolet absorber, a benzotriazole type, a benzophenone type, a cyclic imino ester type, etc., and its combination are mentioned. From the viewpoint of heat resistance, benzotriazole type and cyclic imino ester type are preferable. When two or more types of ultraviolet absorbers are used in combination, ultraviolet rays of respective wavelengths can be absorbed at the same time, thereby further improving the ultraviolet absorbing effect.

Examples of the benzotriazole ultraviolet absorbers include 2- [2'-hydroxy-5 '-(methacryloyloxymethyl) phenyl] -2H-benzotriazole and 2- [2'-hydroxy-5'. -(Methacryloyloxyethyl) phenyl] -2H-benzotriazole, 2- [2'-hydroxy-5 '-(methacryloyloxypropyl) phenyl] -2H-benzotriazole, 2- [ 2'-hydroxy-5 '-(methacryloyloxyhexyl) phenyl] -2H-benzotriazole, 2- [2'-hydroxy-3'-tert-butyl-5'-(methacryloyl Oxyethyl) phenyl] -2H-benzotriazole, 2- [2'-hydroxy-5'-tert-butyl-3 '-(methacryloyloxyethyl) phenyl] -2H-benzotriazole, 2- [2'-hydroxy-5 '-(methacryloyloxyethyl) phenyl] -5-chloro-2H-benzotriazole, 2- [2'-hydroxy-5'-(methacryloyloxyethyl ) Phenyl] -5-methoxy-2H-benzotriazole, 2- [2'-hydroxy-5 '-(methacryloyloxyethyl) phenyl] -5-cyano-2H-benzotriazole, 2 -[2'-hydroxy-5 '-(methacryloyloxyethyl) phenyl] -5-tert-butyl-2H-benzotriazole, 2- [2'-hydroxy-5 '-(methacryloyloxyethyl) phenyl] -5-nitro-2H-benzotriazole and the like, but are not particularly limited thereto.

Examples of the cyclic imino ester ultraviolet absorber include 2,2 '-(1,4-phenylene) bis (4H-3,1-benzoxazin-4-one) and 2-methyl-3,1- Benzoxazine-4-one, 2-butyl-3,1-benzoxazin-4-one, 2-phenyl-3,1-benzoxazin-4-one, 2- (1- or 2-naphthyl ) -3,1-benzoxazin-4-one, 2- (4-biphenyl) -3,1-benzoxazin-4-one, 2-p-nitrophenyl-3,1-benzoxazine- 4-one, 2-m-nitrophenyl-3,1-benzoxazin-4-one, 2-p-benzoylphenyl-3,1-benzoxazin-4-one, 2-p-methoxyphenyl- 3,1-benzoxazin-4-one, 2-o-methoxyphenyl-3,1-benzoxazin-4-one, 2-cyclohexyl-3,1-benzoxazin-4-one, 2 -p- (or m-) phthalimidephenyl-3,1-benzoxazin-4-one, 2,2 '-(1,4-phenylene) bis (4H-3,1-benzoxazinone- 4-one), 2,2'-bis (3,1-benzoxazin-4-one), 2,2'-ethylenebis (3,1-benzoxazin-4-one), 2,2 ' Tetramethylenebis (3,1-benzoxazin-4-one), 2,2'-decamethylenebis (3,1-benzoxazin-4-one), 2,2'-p-phenylenebis (3,1-benzoxazin-4-one), 2,2'- m-phenylenebis (3,1-benzoxazin-4-one), 2,2 '-(4,4'-diphenylene) bis (3,1-benzoxazin-4-one), 2 , 2 '-(2,6- or 1,5-naphthalene) bis (3,1-benzoxazin-4-one), 2,2'-(2-methyl-p-phenylene) bis (3, 1-benzoxazine-4-one), 2,2 '-(2-nitro-p-phenylene) bis (3,1-benzoxazin-4-one), 2,2'-(2-chloro -p-phenylene) bis (3,1-benzoxazin-4-one), 2,2 '-(1,4-cyclohexylene) bis (3,1-benzoxazin-4-one), 1,3,5-tri (3,1-benzoxazine-4-one-2-yl) benzene, 1,3,5-tri (3,1-benzoxazine-4-one-2-yl) Naphthalene, and 2,4,6-tri (3,1-benzoxazin-4-one-2-yl) naphthalene, 2,8-dimethyl-4H, 6H-benzo (1,2-d; 5,4 -d ') bis- (1,3) -oxazine-4,6-dione, 2,7-dimethyl-4H, 9H-benzo (1,2-d; 5,4-d') bis- (1 , 3) -oxazine-4,9-dione, 2,8-diphenyl-4H, 8H-benzo (1,2-d; 5,4-d ') bis- (1,3) -oxazine- 4,6-dione, 2,7-diphenyl-4H, 9H-benzo (1,2-d; 5,4-d ') bis- (1,3) -oxazine-4,6-dione, 6 , 6'-bis (2-methyl-4H, 3,1-benzoxazin-4-one), 6,6'-bis (2-ethyl-4H, 3,1-benzoxa -4-one), 6,6'-bis (2-phenyl-4H, 3,1-benzoxazin-4-one), 6,6'-methylenebis (2-methyl-4H, 3,1- Benzoxazine-4-one), 6,6'-methylenebis (2-phenyl-4H, 3,1-benzoxazin-4-one), 6,6'-ethylenebis (2-methyl-4H, 3,1-benzoxazin-4-one), 6,6'-ethylenebis (2-phenyl-4H, 3,1-benzoxazin-4-one), 6,6'-butylenebis (2 -Methyl-4H, 3,1-benzoxazine-4-one), 6,6'-butylenebis (2-phenyl-4H, 3,1-benzoxazine-4-one), 6,6 ' -Oxybis (2-methyl-4H, 3,1-benzoxazin-4-one), 6,6'-oxybis (2-phenyl-4H, 3,1-benzoxazin-4-one), 6,6'-sulfonylbis (2-methyl-4H, 3,1-benzoxazine-4-one), 6,6'-sulfonylbis (2-phenyl-4H, 3,1-benzoxazine -4-one), 6,6'-carbonylbis (2-methyl-4H, 3,1-benzoxazin-4-one), 6,6'-carbonylbis (2-phenyl-4H, 3 , 1-benzoxazine-4-one), 7,7'-methylenebis (2-methyl-4H, 3,1-benzoxazine-4-one), 7,7'-methylenebis (2-phenyl -4H, 3,1-benzoxazin-4-one), 7,7'-bis (2-methyl-4H, 3,1-benzoxazin-4-one), 7,7'-ethylenebis ( 2-methyl-4H , 3,1-benzoxazin-4-one), 7,7'-oxybis (2-methyl-4H, 3,1-benzoxazin-4-one), 7,7'-sulfonylbis ( 2-methyl-4H, 3,1-benzoxazin-4-one), 7,7'-carbonylbis (2-methyl-4H, 3,1-benzoxazin-4-one), 6,7 '-Bis (2-methyl-4H, 3,1-benzoxazin-4-one), 6,7'-bis (2-phenyl-4H, 3,1-benzoxazin-4-one), 6 , 7'-methylenebis (2-methyl-4H, 3,1-benzoxazine-4-one), and 6,7'-methylenebis (2-phenyl-4H, 3,1-benzoxazine-4 -On) and the like.

When the organic UV absorber is blended into the film, it is exposed to high temperatures in the extrusion process, and therefore, it is preferable to use a UV absorber having a decomposition initiation temperature of 290 ° C or higher to reduce process pollution during film formation. The use of an ultraviolet absorbent having a decomposition initiation temperature of 290 ° C. or lower is not preferable because the decomposition product of the ultraviolet absorbent adheres to a roll group of a manufacturing apparatus or the like during film formation, furthermore, it is reattached to a film or scratches to cause optical defects.

Examples of the inorganic ultraviolet absorbents include ultrafine particles of metal oxides such as cerium oxide, zinc oxide, and titanium oxide.

The upper limit of the melting point is better in terms of heat resistance, but when the polyethylene terephthalate unit is mainly used, the moldability tends to be deteriorated in a film having a melting point exceeding 250 ° C. In addition, transparency tends to deteriorate. In addition, in order to obtain high moldability and transparency, it is preferable to control the upper limit of melting | fusing point to 245 degreeC.

Moreover, in order to improve handling property, such as activity of a film, winding property, etc., it is preferable to form an unevenness | corrugation on a film surface. Generally as a method of forming an unevenness | corrugation on a film surface, the method of containing particle | grains in a film is used.

As said particle | grain, external particle | grains, such as internal precipitation particle | grains, an inorganic particle, and / or organic particle | grains whose average particle diameter is 0.01-10 micrometers, are mentioned. When the particle | grains whose average particle diameter exceeds 10 micrometers are used, defects of a film tend to arise and designability and transparency tend to deteriorate. On the other hand, in the particle | grains whose average particle diameter is less than 0.01 micrometer, there exists a tendency for handling property, such as activity and the winding property of a film, to fall. As for the average particle diameter of the said particle | grain, it is more preferable that a minimum shall be 0.10 micrometer from a viewpoint of handling property, such as activity and windability, Especially preferably, it is 0.05 micrometer. On the other hand, the average particle diameter of the particles is more preferably 5 µm, more preferably 2 µm, in terms of reducing film defects due to transparency and coarse protrusions.

In addition, the average particle diameter of a particle | grain is computed by taking a photograph of multiple sheets of at least 200 particle | grains by the electron microscope method, trace the outline of particle | grains on an OHP film, and convert this trace image into the equivalent circular diameter with an image analyzer.

Examples of the external particles include inorganic particles and styrene such as wet and dry silica, colloidal silica, aluminum silicate, titanium oxide, calcium carbonate, calcium phosphate, barium sulfate, alumina, mica, kaolin, clay, hydroxy apatite, Organic particle | grains etc. which make silicone, acrylic acid, etc. as a component can be used. Among them, inorganic particles such as dry, wet and dry colloidal silica and alumina, and organic particles having styrene, silicone, acrylic acid, methacrylic acid, polyester, divinylbenzene and the like as components are preferably used. These internal particles, inorganic particles and / or organic particles may be used in combination of two or more within a range that does not impair the characteristics defined in the present invention.

Moreover, it is preferable that content in the film of the said particle | grain is 0.001-10 mass%. When it is less than 0.001 mass%, handling property will fall easily, for example, the activity of a film will deteriorate, winding will become difficult. On the other hand, when it exceeds 10 mass%, it becomes easy to cause coarse protrusion formation, film forming property, transparency deterioration, etc.

Moreover, since the refractive index differs from polyester generally, the particle | grains contained in a film become a factor which reduces transparency of a film.

In order to improve designability, a molded article is often printed on the film surface before shape | molding a film. Since such a printed layer is often performed behind a shaping | molding film, it is desired to have high transparency of a film from the viewpoint of print definition.

For this reason, the laminated | multilayer film which has a laminated structure which contained particle | grains only in the surface layer whose thickness is 0.01-5 micrometers, without containing particle | grains substantially in the base film of a main layer, in order to obtain high transparency while maintaining the handleability of a film. It is valid to use. 3 micrometers is preferable and, as for the upper limit of the surface layer thickness, 1 micrometer is especially preferable. In this case, what was illustrated above can be used for particle | grains.

In this invention, in order to make the haze of a film into 0.1 to 3.0%, in the said base film, it does not contain particle | grains substantially, but forms the surface layer of 0.01-5 micrometers in thickness, and has a laminated structure which contained particle only in a surface layer. It is desirable to. Moreover, it is difficult to obtain the film in which a haze becomes 2.0% or less only by containing particle | grains in a film, maintaining handling property.

In addition, the above-mentioned "without particle | grains contained substantially in a base film" means content which becomes below a detection limit, for example, in the case of an inorganic particle, when an inorganic element is quantified by fluorescence X-ray analysis. This is because a contaminant component derived from a foreign substance may be mixed even if particles are not consciously added to the base film.

In order to obtain a film with low haze and high designability, it is preferable not to contain particle | grains substantially in a base film, However, if it is 30 ppm or less, you may add particle | grains in a base film.

Formation of a thin surface layer can be performed by a coating method or a coextrusion method. Especially in the case of a coating method, since adhesiveness with a printing layer can also be improved by using the composition which consists of adhesive modified resin containing particle | grains as a coating layer, it is a preferable method. As said adhesive modified resin, resin which becomes 1 or more types chosen from polyester, a polyurethane, an acrylic polymer, and / or those copolymers is preferable.

As the particles to be contained in the surface layer, the same particles as those described above can be used. Among the particles, silica particles, glass fillers, and silica-alumina composite oxide particles are particularly suitable in terms of transparency because the refractive index is relatively close to polyester.

Moreover, it is preferable that the particle content in the said surface layer is 0.01-25 mass%. When it is less than 0.01 mass%, handling property will fall easily, for example, the activity of a film will deteriorate, or winding will become difficult. On the other hand, when it exceeds 25 mass%, transparency and applicability will deteriorate easily.

In order to provide another function, the polyester film of this invention can be made into a laminated structure by a well-known method using polyester from a different kind. Although the form of such a laminated | multilayer film is not specifically limited, For example, the 2 type 2 layer structure of A / B, the 2 type 3 layer structure of B / A / B structure, and the 3 type 3 layer structure of C / A / B of Laminated form is mentioned.

It is important that the molding polyester film of the present invention is a biaxially oriented film. In the present invention, the thermal strain under the microtension (initial load of 49 mN) of the film can be controlled within the scope of the present invention by molecular orientation by biaxial stretching, and solvent resistance and dimensional stability, which are drawbacks of the unstretched sheet, Is improved. That is, it is one of the characteristics of this invention to improve the solvent resistance and heat resistance which are the drawbacks of an unstretched sheet, maintaining the moldability of an unstretched sheet.

Although the manufacturing method of the said biaxially-oriented polyester film is not specifically limited, For example, after drying a polyester resin as needed, it is supplied to a well-known melt extruder, and it extrudes into a sheet form from a slit-shaped die, etc. A method of biaxially stretching such an unstretched sheet after bringing it into close contact with the casting drum in a manner and by cooling and solidifying to obtain an unstretched sheet (disk) is illustrated.

As a biaxial stretching method, the unstretched sheet is stretched and heat-treated in the longitudinal direction (MD) and the width direction (TD) of a film, and the method of obtaining the biaxially stretched film which has a target in-plane orientation degree is employ | adopted. Among these methods, in terms of film quality, sequential biaxial stretching methods such as the MD / TD method stretching in the longitudinal direction and stretching in the width direction or the TD / MD method stretching in the longitudinal direction after stretching in the width direction. The simultaneous biaxial stretching method of stretching the longitudinal direction and the width direction almost simultaneously is preferable. In the case of the simultaneous biaxial stretching method, a tenter driven by a linear motor may be used. In addition, you may use the multistage extending | stretching method of dividing extending | stretching of the same direction into multiple steps as needed.

As film draw ratio at the time of biaxial stretching, it is preferable to make 1.6-4.2 times in a longitudinal direction and the width direction, Especially preferably, it is 1.7-4.0 times. In this case, either of the stretching magnifications in the longitudinal direction and the width direction may be enlarged or may be the same magnification. As for the draw ratio of the longitudinal direction, it is more preferable to carry out by 2.8 to 4.0 times, and the draw ratio of the width direction to 3.0 to 4.5 times.

As extending | stretching conditions at the time of manufacturing the polyester film for shaping | molding of this invention, it is preferable to employ the following conditions, for example.

In longitudinal stretching, the stretching temperature is more preferably 50 to 110 ° C. and the stretching magnification is 1.6 to 4.0 times so that subsequent lateral stretching can be smoothed.

Usually, when extending | stretching polyethylene terephthalate, when the extending | stretching temperature is low compared with suitable conditions, since the yield stress rises rapidly at the beginning of a lateral stretch, extending | stretching is impossible. Moreover, even if extending | stretching is possible, since it is easy to become nonuniform in thickness and draw ratio, it is unpreferable.

When the stretching temperature is higher than the appropriate conditions, the initial stress is lowered, but the stress is not increased even if the stretching ratio is increased. For this reason, it becomes a film with a small stress at 100% elongation at 25 degreeC. Therefore, by taking the optimal extending | stretching temperature, the film with high orientation can be obtained, ensuring stretchability.

However, when the said copolyester contains 1-40 mol% of copolymerization components, when extending | stretching temperature is raised so that yield stress may be removed, extending | stretching stress will fall rapidly. In particular, since the stress does not increase even in the latter half of the stretching, the orientation does not increase, and the stress at 100% elongation at 25 ° C decreases.

Such a phenomenon is likely to occur at a film thickness of 60 to 500 µm, particularly in a film having a thickness of 100 to 300 µm. For this reason, in the case of the film using the copolymerized polyester of this invention, it is preferable to make extending | stretching temperature of a horizontal direction into the following conditions.

First, preheating temperature is performed in the range of +10 degreeC-+50 degreeC of the glass transition temperature at the time of measuring the mixture (disk) after extruding a film material by an extruder in DSC. Next, in the first half of lateral stretching, the stretching temperature is preferably set to -20 ° C to + 15 ° C relative to the preheating temperature. In the latter half of lateral stretching, the stretching temperature is preferably 0 ° C to -30 ° C with respect to the stretching temperature of the first part, and particularly preferably in the range of -10 ° C to -20 ° C with respect to the stretching temperature of the first part. By employ | adopting such conditions, since the yield stress is small in the first half of lateral stretching, it is easy to extend | stretch and also easy to orientate in the latter half. Moreover, it is preferable to make the draw ratio of a lateral direction 2.5-5.0 times. As a result, it is possible to obtain a film that satisfies F100 ₂₅ or F100 ₁₀₀ defined in the present invention.

After the biaxial stretching, the film is subjected to heat treatment (thermal fixation treatment). These heat treatment conditions are important conditions for achieving both haze and surface roughness, that is, film activity. Although the film after completion | finish of extending | stretching continues heat processing in a tenter, in this case, it is important to divide heat processing into 2 or more steps. The heat treatment temperature TS1 of the first stage is in the range of -5 ° C to -30 ° C of the heat treatment temperature TS2 of the second stage, and the lower limit is preferably TS2-10 ° C, and the upper limit is preferably TS2-25 ° C. The heat treatment temperature TS2 of 2nd stage | paragraph is performed in the range of -5 degreeC--35 degreeC of melting | fusing point at the time of measuring the mixture (disk) after extruding a film material by an extruder in DSC mentioned later. Preferably the lower limit of TS2 is 10 degreeC of melting | fusing point, and the upper limit of TS2 becomes like this. Preferably it is melting | fusing point -30 degreeC. It is also possible to provide an intermediate heat treatment zone between TS1 and TS2, or to provide a heat treatment zone after TS2. In these cases, TS2 exhibits the highest heat treatment temperature. By taking such conditions, a film with low haze and good activity can be obtained.

The heat treatment may be either tension heat treatment or relaxation heat treatment. In order to lower thermal contraction rate, 3-10% of loosening heat treatment is preferable.

The reason is considered as follows. The polyester film containing about 5-50 mol% of copolymerization components like this invention has a low crystallization rate and low crystallinity compared with a polyethylene terephthalate film etc. For this reason, if heat processing is rapidly performed at high temperature after completion | finish of extending | stretching, the mobility of the molecule | numerator which comprises a material with low crystallinity in a heat processing zone will become high. Therefore, since the surface protrusion formed by raising the particles (particles in the film and / or particles of the coating layer) in the stretching step is buried again in the heat treatment zone, sufficient surface roughness cannot be obtained. For this reason, in order to wind up a film neatly, content of particle | grains is made to increase more than the required amount of a polyethylene terephthalate film, and it becomes a cause which a haze deteriorates. On the other hand, when the temperature of TS2 is lower than predetermined temperature, the film with the low thermal contraction rate in 150 degreeC will not be obtained sufficiently.

Therefore, taking the method of the present invention having the heat treatment zone in two stages (or more) promotes the crystallization of the film to some extent before the particles are buried inside the film in TS1, and increases the temperature sufficiently in the TS2 zone. Moreover, compared with the state of the preceding claim, the motility of a molecule | numerator is fully reduced, the crystal | crystallization is further promoted with the processus | protrusion of a surface, and the film with low thermal contraction rate is obtained. In addition, it is possible to prevent the addition of more than necessary particles.

Generally, as a means of lowering the plane orientation, a method of lowering the draw ratio and increasing the blending amount of the copolymerization components is known. In the former method, the film thickness nonuniformity is deteriorated, and in the latter method, the melting point of the film is lowered. It is not preferable because the heat resistance deteriorates. In the present invention, heat setting is performed at a higher temperature than usual in order to reduce the surface orientation of the biaxially oriented polyester film and the heat shrinkage at 150 ° C. It is preferable to perform heat setting in the above-mentioned heat processing, especially the 2nd-stage heat processing.

In addition, in this invention, it is necessary to use a copolyester as a biaxially-oriented polyester film, and since melting | fusing point is low compared with a homogeneous polymer, when heat setting temperature is made high, a film will fuse to the clip which hold | maintains a film in a lateral stretch process. It becomes difficult to peel off. Therefore, it is important to cool the vicinity of the clip sufficiently when the clip opens the film at the tenter exit. Specifically, in order to make it easy to peel a film and a clip, (1) the method of installing a heat shielding wall in a clip part so that a clip is hard to heat, (2) the method of adding a clip cooling mechanism to a tenter, (3) In order to enhance the cooling capacity, the cooling section after heat setting is set long to sufficiently cool the entire film, and (4) the method of increasing the cooling efficiency by increasing the length and number of sections of the cooling section, (5 It is preferable to employ a method of enhancing cooling of the clip by using a type in which the return portion of the clip travels outside the furnace.

As described above, by using the polyester film for molding according to the present invention, it is difficult to mold with a conventional biaxially oriented polyester film, such as vacuum molding or press molding at a low pressure of 10 atm or less. Also in the molding method, a molded article having good finish can be obtained. Moreover, since these molding methods are inexpensive molding cost, they are superior in the economics in manufacture of a molded article. Therefore, what is applied to these shaping | molding methods can exhibit the effect of the molding polyester film of this invention most effectively.

On the other hand, mold molding is disadvantageous in terms of economical efficiency due to the high cost of a mold and a molding apparatus, but has a feature that molded articles having a more complicated shape than the above molding method are molded with high precision. For this reason, when molding using the polyester film for molding of the present invention, compared with the conventional biaxially oriented polyester film, it is possible to mold at a lower molding temperature, and the remarkable effect that the finish of the molded article is improved is improved. Expressed.

In addition, the molded article thus formed is excellent in elasticity and form stability (heat shrinkage characteristics, thickness nonuniformity) when used in a room temperature atmosphere, excellent solvent resistance and heat resistance, and low environmental load. It can be used suitably as a molding member, such as a nameplate, a model can, a building material, a makeup board, a makeup steel plate, and a transfer sheet.

In addition to the above molding method, the molding polyester film of the present invention is also suitable as a molding material to be molded using a molding method such as press molding, laminate molding, in-mold molding, drawing molding or bending molding.

(Polyester Film for Molding with Hard Coat Layer)

Another aspect of the present invention is a molding polyester film in which a hard coat layer is provided on at least one surface of the molding polyester film directly or via a surface layer made of an adhesive improvement resin. In this invention, in order to supplement the surface hardness of the base material used as a polyester film for shaping | molding, and to improve abrasion resistance, the hard coat layer shows the layer which has a film of higher hardness than a base material.

Although the layer which has hard coat property which can be used by this invention is not specifically limited, Melamine type | system | group, acryl type, silicone type hard coat etc. can be used, but an acryl-type hard coat layer is preferable at the point from which a hard hard coat film is obtained.

As a preferable aspect of the acryl-type hard-coat layer in this invention, after apply | coating the coating agent containing the polyfunctional (meth) acrylate compound which has two or more (meth) acryloyl groups in 1 molecule, superposition | polymerization and / or The film made of resin is used preferably by making it react. 1 type may be sufficient as a polyfunctional (meth) acrylate compound, and 2 or more types may be mixed and used for it.

Two or more (meth) acryloyl groups (However, the description of the "(meth) acryloyl group" in this invention abbreviated and displayed the acryloyl group or the methacryloyl group in 1 molecule in this invention. As the polyfunctional (meth) acrylate compound having the above formula, a compound in which the hydroxyl group of the polyhydric alcohol having two or more alcoholic hydroxyl groups in one molecule is an esterified product of two or more (meth) acrylic acids can be used.

In particular, the hard coat layer is formed with a coating agent containing a polyfunctional (meth) acrylate monomer compound having two (meth) acryloyl groups in one molecule and a monomer compound having three or more (meth) acryloyl groups in one molecule. It is preferable to form because it is excellent in scratch resistance and flexibility as well as hardness and hardenability.

Specifically as a polyfunctional (meth) acrylate compound which has two (meth) acryloyl groups in 1 molecule, (a) (meth) acrylic-acid diester of C2-C12 alkylene glycol: ethylene glycol di (meth) ) Acrylate, propylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, b) (meth) acrylic acid diesters of polyoxyalkylene glycol: diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, dipropylene (Meth) acrylic acid diesters of (c) polyhydric alcohols, such as glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, and polypropylene glycol di (meth) acrylate: pentaerythritol di (meth) (Meth) acrylic acid diesters of ethylene oxide and propylene oxide adduct of (d) bisphenol A or a hydride of bisphenol A, such as an acrylate: 2,2'-bis (4-acryloxyethoxyphenyl) propane (E) A terminal isocyanate group-containing compound obtained by reacting a diisocyanate compound with two or more alcoholic hydroxyl group-containing compounds in advance such as 2,2'-bis (4-acryloxypropoxyphenyl) propane, further containing an alcoholic hydroxyl group ( Acrylic acid or methacrylic acid is reacted with the urethane (meth) acrylate which has two or more (meth) acryloyloxy groups in the molecule | numerator obtained by making a methacrylate react, and the compound which has two or more epoxy groups in (f) molecule | numerator. And epoxy (meth) acrylates having two or more (meth) acryloyloxy groups in the molecule obtained.

Specific examples of the monomer compound having three or more (meth) acryloyl groups in one molecule include pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol tri (meth) acrylate, and dipenta Erythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, trimethylolpropane tri (meth) acrylate, and the like. Moreover, the urethane acrylate compound which has three or more (meth) acryloyl groups in 1 molecule, and the epoxy acrylate compound which has three or more (meth) acryloyl groups in 1 molecule is mentioned.

As for the usage ratio of the monomer which has three or more (meth) acryloyl groups in these 1 molecule, 30-90 mass% is preferable with respect to solid content total amount. When the use ratio of the monomer is less than 30% by mass, a hardened film having sufficient scratch resistance is hardly obtained, and when the amount exceeds 90% by mass, not only the flexibility of the film is lowered, but also the hard coat during molding. It is not preferable because cracks occur in the layer.

As a method of polymerizing and / or reacting the compound composition of the hard coat layer, a method of irradiating electron beams, radiation, and ultraviolet rays may be used. In the case of ultraviolet irradiation, it is preferable to add a photopolymerization initiator to the composition.

Specific examples of the photopolymerization initiator include acetophenone, 2,2-diethoxyacetophenone, p-dimethylacetophenone, p-dimethylaminopropiophenone, benzophenone, 2-chlorobenzophenone, 4,4'-dichlorobenzophenone, 4,4'-bisdiethylaminobenzophenone, Michler's ketone, benzyl, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, methylbenzoyl formate, p-isopropyl-α-hydride Carbonyl compounds, such as oxyisobutyl phenone, the (alpha)-hydroxy isobutyl phenone, 2, 2- dimethoxy- 2-phenylacetophenone, and 1-hydroxy cyclohexyl phenyl ketone, tetramethyl thiuram monosulfide, tetramethyl Sulfur compounds such as thiuram disulfide, thioxanthone, 2-chlorothioxanthone and 2-methyl thioxanthone, and peroxide compounds such as benzoyl peroxide and di-t-butyl peroxide. These photoinitiators may be used independently and may be combined 2 or more types. The amount of the photopolymerization initiator added is in the range of 0.01 to 10% by mass of the solid content, and when the amount is small, the reaction is slow, resulting in poor productivity, and sufficient hard coatability is not obtained by the remaining unreacted material. On the contrary, when the addition amount is large, a problem occurs that the hard coat layer is yellowed by the photoinitiator.

Compounds for forming the hard coat layer used in the present invention include known thermal polymerization inhibitors such as hydroquinone, hydroquinone monomethyl ether, and 2,5-t-butylhydroquinone in order to prevent thermal polymerization during production and dark reaction during storage. Preference is given to adding. As for the addition amount of a thermal-polymerization inhibitor, 0.005-0.05 mass% is preferable in solid content.

The organic solvent can be mix | blended with the compound composition which forms the hard-coat layer used for this invention in the range which does not impair the objective of this invention for the purpose of the improvement of workability at the time of coating, and adjustment of a coating film thickness.

As an organic solvent, since the drying temperature after application | coating needs to be adjusted to 150 degrees C or less from the heat resistance problem of the molding polyester film used as a base material, it is preferable that a boiling point is 50-150 degreeC. Specific examples include alcohol solvents such as methanol, ethanol and isopropyl alcohol, acetate ester solvents such as methyl acetate, ethyl acetate and butyl acetate, ketone solvents such as acetone and methyl ethyl ketone, aromatic solvents such as toluene and dioxane Cyclic ether solvents, such as these, etc. are mentioned. These solvents can also be used individually or in mixture of 2 or more types.

Various additives can be mix | blended with the hard coat layer of this invention as needed. Examples thereof include fillers for imparting surface irregularities and relaxation of internal stress, fluorine and silicon compounds for imparting water repellency, leveling agents and antifoaming agents for improving coating properties and appearance, and further, coloring dyes and pigments.

Although a hard coat layer may be apply | coated after a molding process, it is preferable to laminate | stack on the film before shaping | molding process which can be processed continuously in a roll form. Although a well-known method is mentioned as a method of laminating | stacking, a spray method, a dip (dip) method, a roll coating method, the die coating method, the gravure coating method, etc. are mentioned specifically ,.

The thickness of the hard coat layer is preferably 0.5 µm or more and 10 µm or less. When the thickness is thin, hard coat property is hardly obtained, whereas when thick, the curl due to hardening shrinkage tends to be bad. Especially preferable thickness is 1 micrometer or more and 6 micrometers or less.

The molded film provided with the hard coat layer of the present invention has a good moldability and a good finish, and a molded article excellent in scratch resistance of the surface can be easily obtained. It can be used suitably as a molding member, such as a can, a building material, a makeup board, and a makeup steel board.

Hereinafter, an Example demonstrates this invention in detail. In addition, the film characteristic obtained by each Example was measured and evaluated by the following method.

(1) intrinsic viscosity

0.1 g of the chip sample was precisely weighed, dissolved in 25 ml of a mixed solvent of phenol / tetrachloroethane = 60/40 (mass ratio), and measured at 30 ° C using an Ostwald viscometer. In addition, the measurement was performed 3 times and the average value was calculated | required.

(2) thickness non-uniformity

A continuous tape-like sample of a film having a length of 3 m in the transverse stretching direction and a width of 5 cm in the longitudinal stretching direction is wound up, and the film thickness is measured with a film thickness continuous measuring instrument (manufactured by Anritsu Co., Ltd.) and recorded in the recorder. The maximum value Tmax, minimum value Tmin, and average value Tav of thickness were calculated | required from the chart, and thickness nonuniformity (%) was computed by the following formula. In addition, the measurement was performed 3 times and the average value was calculated | required. In the case where the length in the transverse stretching direction is less than 3 m, they are connected together. In addition, the measurement data in the connection part was deleted.

Thickness nonuniformity (%) = ((Tmax-Tmin) / Tav) × 100

(3) Hayes

In accordance with JIS-K7136-2000, the haze of the film was measured using the haze meter (300A of Nippon Denshoku Industries Co., Ltd. make). In addition, the measurement was performed twice and the average value was calculated | required.

(4) film thickness

Using millitron, 5 points per sheet and 15 points in total of 3 sheets were measured, and the average value was obtained.

(5) 100% elongation at break and elongation at break

With respect to the longitudinal direction and the width direction of the biaxially oriented film, the sample was cut out with a single blade razor in a rectangular shape having a length of 180 mm and a width of 10 mm, respectively. Subsequently, a rectangular sample was stretched using a tensile tester (manufactured by Toyo Seiki Co., Ltd.), and the stress (MPa) and elongation at break (%) at 100% elongation in each direction were determined from the obtained load-distortion line.

In addition, the measurement was carried out under the conditions of an initial length (distance between marks) of 40 mm, a distance between the chucks, 100 mm, a crosshead speed of 100 mm / min, a chart speed of 200 mm / min, and a load cell of 25 kgf in an atmosphere of 25 ° C. It was done. In addition, this measurement was performed 10 times and the average value was used.

Moreover, the tension test was done on the conditions similar to the above also in 100 degreeC atmosphere. At this time, the sample was measured after maintaining for 30 second in 100 degreeC atmosphere. In addition, the measurement was performed 10 times and the average value was used.

(6) surface roughness (Ra)

Based on JIS-B601-2001, Ra of the film was measured by sulfcom 304B (made by Tokyo Seimitsu Co., Ltd.). In addition, the measurement conditions were performed at 0.08 micrometers of cutoffs, a needle radius of 2 micrometers, a measuring length of 0.8 mm, and a measuring speed of 0.03 mm / second.

(7) heat shrinkage rate at 150 ° C

The rectangular sample of length 150mm and width 20mm is cut out with respect to the longitudinal direction and the width direction of a film, respectively. Two marks are given at intervals of 100 mm in the longitudinal direction of each sample, and the distance A between the two marks is measured under no load. Subsequently, one of each rectangular sample is suspended in a basket with a clip under no load, and placed in a gear oven under a 150 ° C atmosphere, and the time is measured. After 30 minutes, the basket is taken out of the gear oven and left to stand at room temperature for 30 minutes. Subsequently, the interval B is read out for each sample under no load. The thermal contraction rate in 150 degreeC of each sample is calculated from the following space | interval A and B by the following formula.

Thermal Shrinkage (%) = ((A-B) / A) × 100

(8) Surface orientation (△ P)

Using a sodium D-ray (wavelength 589 nm) as a light source, a refractive index (Nz) in the longitudinal direction, a refractive index (Ny) in the width direction and a refractive index (Nz) in the thickness direction were measured using an Abbe refractometer and The orientation degree (ΔP) was calculated.

ΔP = ((Nx + Ny) / 2) -Nz

(9) Light transmittance at wavelength 370 nm

Using the spectrophotometer (manufactured by Shimadzu Seisakusho Co., Ltd., UV-1200), the light transmittance of the film in the ultraviolet region having a wavelength of 370 nm was measured.

(10) Unwinding property of roll-shaped film

The film formed into a film is wound around a 3-inch paper tube 300 mm wide x 200 m long, and left to stand for 72 hours under a 23 ° C 65 RH% atmosphere. Then, when the film was installed in a vacuum evaporator and unwound at a speed of 50 m / min in the atmosphere of 1x10 <^-4> torr, the following evaluation was performed until it rewound. As for the criterion of determination, (circle) and the case where there is more than one problem, it made x that there was no problem from every viewpoint.

a. Tearing of the film

b. The occurrence of stickiness

c. Generation of loud sounds due to friction between films or between films / rolls

(11) Glass transition temperature (Tg) and melting point (Tm) of raw materials (objects)

About 7 mg of the raw material extruded on the conditions of each Example was put into the sample pan using the differential scanning calorimetry apparatus (DSC3100S by McScience Co., Ltd.), and the lid of the pan was closed and 20 degreeC from room temperature to 300 degreeC in nitrogen gas atmosphere. It measured by heating up at the temperature increase rate of / min. Tg (° C.) was determined based on JIS-K7121-1987, 9-3, and the melting point was determined by the melting peak temperature (Tpm) defined in 9-1.

Melting | fusing point of a biaxially-oriented polyester film is also measured similarly, and a melting peak temperature (Tpm) is calculated | required.

(12) light resistance

In the dark box, the offset-printed print sample was placed at the position of 3 cm immediately below the fluorescent lamp lamp (manufactured by Matsushita Electric Co., Ltd., U-type fluorescent lamp FUL9EX) so that the printing surface of the print sample was rearward. Subsequently, light irradiation was performed for 2000 hours continuously, and the color difference ((DELTA) E value) was measured based on the color (a *, b *, L *) before and behind the light irradiation on the printing surface side, based on JISZ8730. The smaller the color difference (ΔE value), the smaller the change in color before and after light irradiation, that is, the better light resistance. The acceptance level of light resistance is 0.5 or less in color difference ((DELTA) E value). In addition, the color difference (ΔE value) is calculated by the following equation.

△ E = √ (△ a ² + △ b ² + △ L ² )

(13) formability

(a) vacuum forming

After 5 mm square printing was performed on the film, the film was heated for 10 to 15 seconds with an infrared heater heated to 500 ° C, and vacuum molding was performed at a mold temperature of 30 to 100 ° C. In addition, heating conditions selected the optimum conditions within the said range about each film. The shape of the mold was cup, the opening was 50 mm in diameter, the bottom was 40 mm in diameter, 50 mm in depth, and all corners were curved to 0.5 mm in diameter.

The moldability and the finishability were evaluated about five molded articles vacuum-molded under optimal conditions, and the ranking was performed based on the following reference | standard. In addition, (circle) and (circle) were made pass and x was rejected.

◎: (성형) There is no tear in the molded article,

  (Ii) the radius of curvature of the corner is 1 mm or less, and the printing shift is 0.1 mm or less;

  (Iii) no appearance defects corresponding to ×

○: (m) there is no tear in the molded article,

  (Ii) the radius of curvature of the corner is more than 1 mm and 1.5 mm or less, or the printing deviation is more than 0.1 mm and 0.2 mm or less,

  (Iii) In addition, there is no appearance defect corresponding to x and is a level practically without a problem.

X: The thing corresponded to any one of the following items (i)-(iv) even if there exists a tear in a molded article, or there is no tear

  (Ⅰ) The radius of curvature of the corners exceeds 1.5 mm

  (Ii) bad appearance due to large wrinkles

  (Ⅲ) Whitening of film, resulting in reduced transparency

  (Iii) The deviation of printing exceeds 0.2 mm

 (b) formation of pressure

After 5 mm square printing was performed on the film, the film was heated for 10 to 15 seconds with an infrared heater heated to 500 ° C., and then press-molded under pressure of 4 atm at a mold temperature of 30 to 100 ° C. In addition, heating conditions selected the optimum conditions within the said range about each film. The shape of the mold was cup-shaped, the opening was 60 mm in diameter, the bottom was 55 mm in diameter, 50 mm in depth, and all corners were curved to 0.5 mm in diameter.

The moldability and finish are evaluated about five molded articles vacuum-molded under optimal conditions, and the ranking is performed based on the following reference | standard. In addition, (circle) and (circle) were made pass and x was rejected.

◎: (성형) There is no tear in the molded article,

  (Ii) the radius of curvature of the corner is 1 mm or less, and the printing shift is 0.1 mm or less;

  (Iii) no appearance defects corresponding to ×

○: (m) there is no tear in the molded article,

  (Ii) the radius of curvature of the corner is more than 1 mm and 1.5 mm or less, or the printing deviation is more than 0.1 mm and 0.2 mm or less,

  (Iii) In addition, there is no appearance defect corresponding to x and is a level practically without a problem.

X: The thing corresponded to any of the following items (i)-(iii) even if there is a tear in a molded article, or there is no tear

  (Ⅰ) The radius of curvature of the corners exceeds 1.5 mm

  (Ii) bad appearance due to large wrinkles

  (Iii) the film is whitened and the transparency is lowered

  (Iii) The deviation of printing exceeds 0.2 mm

(c) mold forming

After printing on the film, contact heating was performed on a hot plate heated to 100 to 140 ° C. for 4 seconds, and press molding was performed at a mold temperature of 30 to 70 ° C. and a holding time of 5 seconds. In addition, heating conditions selected the optimum conditions within the said range about each film. The shape of the mold was cup-shaped, the opening was 50 mm in diameter, the bottom was 40 mm in diameter, 30 mm in depth, and all corners were curved to 0.5 mm in diameter.

The moldability and the finishability were evaluated about five molded articles molded under optimum conditions, and the ranking was performed based on the following criteria. In addition, (circle) and (circle) were made pass and x was rejected.

◎: (성형) There is no tear in the molded article,

  (Ii) the radius of curvature of the corner is 1 mm or less, and the printing shift is 0.1 mm or less;

  (Iii) no appearance defects corresponding to ×

○: (m) there is no tear in the molded article,

  (Ii) the radius of curvature of the corner is more than 1 mm and 1.5 mm or less, or the printing deviation is more than 0.1 mm and 0.2 mm or less,

  (Iii) In addition, there is no appearance defect corresponding to x and is a level practically without a problem.

X: The thing corresponded to any of the following items (i)-(iii) even if there is a tear in a molded article, or there is no tear

  (Ⅰ) The radius of curvature of the corners exceeds 1.5 mm

  (Ii) bad appearance due to large wrinkles

  (Iii) the film is whitened and the transparency is lowered

  (Iii) The deviation of printing exceeds 0.2 mm

(14) solvent resistance

The sample was immersed in toluene temperature-controlled at 25 degreeC for 30 minutes, and it judged with the following reference | standard about the external appearance change before and behind immersion, and made (circle) the pass. In addition, haze value was measured by the said method.

○: almost no change in appearance and less than 1% change in haze value

X: Appearance change is confirmed, or the change of a haze value is 1% or more

(15) Printing quality

The film before printing was heat-processed at 90 degreeC for 30 minutes, and then screen printing of four colors was performed.

Furthermore, the film provided with the printing layer was dried at 80 degreeC for 30 minutes. Evaluation of the printing quality judged visually the printing appearance, such as the following feeling of clearness, printability, and a printing shift, through the film from behind rather than from a printing surface. As for the criterion of determination, (circle) the thing which did not have a problem from all the viewpoints, (triangle | delta) which has a problem in one or more aspects, and the thing which has a problem in two or more aspects was made into x.

a. Clear feeling: The printed pattern is clearly seen without being blocked by the base film or the coating layer.

b. Printability: No color unevenness or omission due to transfer defect of printing ink

c. Print discrepancy: The discrepancy of print cannot be discriminated with the naked eye.

(16) scratch resistance

In accordance with JIS-K5600, the surface was reciprocated 20 times with steel wool of # 0000 at a load of 1 kgf, and left for 24 hours, and then visually evaluated.

Example 1

Chips of copolymerized polyester having an intrinsic viscosity of 0.69 dl / g having 100 mol% of terephthalic acid units as aromatic dicarboxylic acid components, 40 mol% of ethylene glycol units and 60 mol% of neopentylglycol units as diol components ( A) and 0.04 mass% of amorphous silica having an intrinsic viscosity of 0.69 dl / g and an average particle diameter (SEM method) of 1.5 µm, and a benzotriazole-based ultraviolet absorber (N) (made by Ciba-Specialty Chemicals Co., Ltd.) And Chip (B) of polyethylene terephthalate containing 0.67% by mass of thybinin 326 were dried. In addition, the chip A and the chip B were mixed so as to have a mass ratio of 25:75. These chip mixtures were then melt-extruded from the slits of the T die with an extruder at 270 ° C., quenched and solidified on a chill roll at a surface temperature of 40 ° C., while the amorphous unstretched sheet was brought into close contact with the chill roll using electrostatic application. Got it.

The obtained unstretched sheet was stretched 3.3 times at 90 degreeC in the longitudinal direction between a heating roll and a cooling roll. Subsequently, the uniaxial stretched film was guide | induced to the tenter, it preheated at 120 degreeC for 10 second, and the first half of lateral stretch was extended 3.9 times at 110 degreeC, and the latter half at 100 degreeC. Further, the biaxially stretched polyester film having a thickness of 100 μm was subjected to heat setting at 235 ° C. while the first step of heat treatment TS1 was performed at 205 ° C. and the second step of heat treatment TS 2 was performed at 7% in the transverse direction. Got.

In addition, an intermediate section of 2 m is installed in the heat setting zone between the stretching section, and a far-infrared heater is installed in the heating section of the heat setting zone, expanding the shielding plate to the limit position where the film does not contact the film. Was installed. In the cooling section after heating, the section shielding is reinforced, and an external return method is used as the clip return method, and a clip cooling device is installed, and forced cooling by cold wind of 20 ° C, and the clip temperature at the tenter outlet is 40 ° C. The following clip fusion prevention measures were performed.

Comparative Example 1

In Example 1, the biaxially stretched polyester film was obtained like Example 1 except having changed the heat setting temperature in TS1 and TS2 to 235 degreeC.

Comparative Example 2

In Example 1, the biaxially stretched polyester film was obtained like Example 1 except having changed the heat setting temperature in TS1 and TS2 to 205 degreeC.

Example 2

In Example 1, the biaxially stretched polyester film was obtained like Example 1 except having changed the chip (B) into the polyethylene terephthalate chip (C) which does not contain a ultraviolet absorber.

Example 3

(Adjustment of coating amount)

Water-soluble urethane resin which blocked 3.15 mass% and terminal isocyanate group by the hydrophilic group by copolymerization polyester resin (Toyo Boseki Co., Ltd., Vironal MD-1250) in solid content in 40 mass% aqueous solution of isopropanol (Daiichi Kogyo Pharmaceutical Co., Ltd.) (Elastron H-3) as a solid to contain 5.85% by mass of silica particles having an average particle diameter of 1.0 μm and 0.8% by mass of all resins and 10% by mass of silica particles having an average particle diameter of 0.05 μm. And the coating liquid were adjusted. The obtained coating liquid was adjusted to pH 6.5 using 5 mass% aqueous sodium bicarbonate solution. Subsequently, it filtered with a bag filter (Sumitomo 3M Co., Ltd., liquid filter bag), and stirred for 2 hours at 15 degreeC in the coating liquid circulation system stock tank.

The following chips (D), (J) and (F) were prepared as film raw materials of Example 3.

Chip (D) is a benzotriazole-based ultraviolet absorber (a resin component is composed of 100 mol% terephthalic acid units as aromatic dicarboxylic acid components, 70 mol% ethylene glycol units and 30 mol% neopentyl glycol units as diol components). N) (Ciba Specialty Chemicals Co., Ltd., Tinuvin 326) is a chip of a copolymer polyester having an intrinsic viscosity of 0.77 dl / g.

Chip J is a polyethylene terephthalate chip having an intrinsic viscosity of 0.77 dl / g, which contains 0.67 mass% of a benzotriazole ultraviolet absorber (N) (Ciba Specialty Chemicals Co., Ltd., Tinuvin 326).

Chip (F) is a polypropylene terephthalate (PPT) having a intrinsic viscosity of 0.75 dl / g, containing 0.67 mass% of a benzotriazole ultraviolet absorber (N) (Ciba Specialty Chemicals, Tinuvin 326). Chip.

After drying each said chip, the chip | tip D, the chip | tip J, and the chip | tip F were mixed so that it might become a mass ratio of 50:10:40. These chip mixtures were then melt extruded from a slit of the T die at 270 ° C. by an extruder and rapidly solidified on a chill roll at a surface temperature of 40 ° C., while simultaneously adhering to the chill roll using an electrostatic application method while the amorphous unstretched sheet. Got.

The obtained unstretched sheet was stretched 3.5 times at 83 degreeC in the longitudinal direction between a heating roll and a cooling roll. Next, the said coating liquid was apply | coated to the chill roll surface side (F surface) of a uniaxial stretched film so that the thickness of resin solid content before extending | stretching might be set to 0.9 micrometer by the reverse kiss coat method. The laminated | multilayer film which has an application layer was guide | induced to tenter, drying, it preheated at 95 degreeC for 10 second, and extended | stretched the first half of lateral stretch at 80 degreeC, and the latter half at 3.9 times at 75 degreeC. In addition, a biaxially stretched polyester film having a thickness of 50 μm was subjected to a heat setting treatment at 210 ° C. while performing a thermal treatment at 190 ° C. for the first stage of heat treatment TS1 at 190 ° C., and a 7% relaxation treatment for the second stage of heat treatment TS2 in the lateral direction. Got.

In addition, an intermediate section of 2 m is installed in the heat-setting zone between the stretching section, and a far-infrared heater is installed in the heating section of the heat-setting zone, expanding the shielding plate for each section to the limit position where it does not contact the film. Was installed. In the cooling section after heating, the section shielding is reinforced, and an external return method is used as the clip return method, and a clip cooling device is installed, and forced cooling by cold wind of 20 ° C, and the clip temperature at the tenter outlet is 40 ° C. The following clip fusion prevention measures were performed.

Comparative Example 3

In Example 3, the biaxially stretched polyester film was obtained like Example 3 except having changed the heat setting temperature in TS1 and TS2 to 205 degreeC.

Comparative Example 4

In Example 3, the biaxially stretched polyester film was obtained like Example 2 except having changed the heat setting temperature into 180 degreeC (TS1) and 220 degreeC (TS2).

Example 4

The raw material structure of Example 3 was used as a core layer, and as a raw material for skin layers, the chip | tip which mixed the chip | tip D and the chip | tip J at 50:50 mass ratio was thrown into another extruder, and it melt | dissolves at 280 degreeC, and core layer And the biaxially stretched poly in the same manner as in Example 2, except that the raw material was bonded to a feed block such that the skin layer / core layer / skin layer was 10/80/10, and then extruded from a T-die at 270 ° C. An ester film was obtained.

Example 5

As a raw material of Example 5, the following chip (O) and chip (P) were prepared in addition to the chip (J).

Chip (O) is a copolymer having an intrinsic viscosity of 0.71 dl / g comprising 60 mol% of terephthalic acid units, 40 mol% of isophthalic acid units as the aromatic dicarboxylic acid component, and 100 mol% of ethylene glycol units as the diol component. It is a chip of polyester.

Chip P has an intrinsic viscosity of 0.71 dl / with 60 mol% of terephthalic acid units and 40 mol% of naphthalenedicarboxylic acid components as aromatic dicarboxylic acid components and 100 mol% of ethylene glycol units as diol components. g is a chip of copolyester.

The chip | tip (J), the chip | tip (O) of said copolyester, and the chip | tip (P) of polyethylene terephthalate were mixed so that it might become a mass ratio of 50:25:25, and it dried. These chip mixtures were then melt-extruded from the slits of the T die with an extruder at 270 ° C., quenched and solidified on a chill roll at a surface temperature of 40 ° C., while the amorphous unstretched sheet was brought into close contact with the chill roll using electrostatic application. Got it.

The obtained unstretched sheet was stretched 3.5 times at 90 degreeC in the longitudinal direction between a heating roll and a cooling roll. Subsequently, the uniaxial stretched film was guide | induced to the tenter, it preheated at 120 degreeC for 10 second, and the first half of lateral stretch was extended 3.9 times at 110 degreeC, and the latter half at 100 degreeC. In addition, a biaxially stretched polyester film having a thickness of 100 μm was subjected to a heat setting treatment at 238 ° C. while performing a heat treatment at 205 ° C. and a second heat treatment (TS 2) at 205 ° C. in the transverse direction. Got.

In addition, an intermediate section of 2 m is installed in the heat-setting zone between the stretching section, and a far-infrared heater is installed in the heating section of the heat-setting zone, expanding the shielding plate for each section to the limit position where it does not contact the film. Was installed. In the cooling section after heating, the section shielding is strengthened, and an external return method is used as the clip return method, and a clip cooling device is installed, forcibly cooled by 20 ° C cold wind, and the clip temperature at the tenter outlet is 40 ° C. The following clip fusion prevention measures were performed.

Example 6

Chip of copolyester polyester having intrinsic viscosity of 0.69 dl / g having 100 mol% of terephthalic acid units as aromatic dicarboxylic acid component, 40 mol% of ethylene glycol units and 60 mol% of neopentylglycol units as constituent components (A ) And a chip (I) of polybutylene terephthalate containing 0.04 mass% of amorphous silica having an intrinsic viscosity of 1.00 dl / g and an average particle diameter (SEM method) of 1.5 µm.

Subsequently, the chip (A), the chip (I), and the benzotriazole type ultraviolet absorber (N) (Ciba Specialty Chemicals Co., Ltd., Tinuvin 326) were mixed so that it might become a mass ratio of 25.0: 74.5: 0.5. These mixtures were then melt-extruded from the slits of the T die with an extruder at 265 ° C. and rapidly solidified on a chill roll at a surface temperature of 20 ° C., while simultaneously contacting the chill roll using an electrostatic application method to obtain an amorphous unstretched sheet. .

The obtained unstretched sheet was stretched 3.3 times at 80 ° C. in the longitudinal direction between the heating roll and the cooling roll. Subsequently, the uniaxial stretched film was guide | induced to the tenter, it preheated at 95 degreeC for 10 second, and extended | stretched the first half of lateral stretch to 85 degreeC, and the latter half to 3.8 times at 80 degreeC. In addition, a biaxially stretched polyester film having a thickness of 100 μm was subjected to a heat setting treatment at 200 ° C. while performing a 7% relaxation treatment at 185 ° C. and a second heat treatment TS 2 in the horizontal direction. Got.

In addition, an intermediate section of 2 m is installed in the heat-setting zone between the stretching section, and a far-infrared heater is installed in the heating section of the heat-setting zone, expanding the shielding plate for each section to the limit position where it does not contact the film. Was installed. In the cooling section after heating, the section shielding is strengthened, and an external return method is used as the clip return method, and a clip cooling device is installed, forcibly cooled by 20 ° C cold wind, and the clip temperature at the tenter outlet is 40 ° C. The following clip fusion prevention measures were performed.

About Examples 1-6 and Comparative Examples 1-4, the raw material composition and polymer characteristic of the used polymer are shown in Table 1, and the manufacturing conditions and the characteristic of a film are shown in Tables 2-5.

Example 7

The following hard coat coating liquid was applied onto the polyester film for molding obtained in Example 3 so as to have a thickness of 3 占 퐉 after drying by a microgravure method, dried by hot air at 80 ° C, and a high pressure mercury lamp having an output of 160 W / cm. The bottom 20 cm position was passed through at a speed of 30 m / min, and the molding polyester film which provided the hard-coat layer was obtained. The moldability (vacuum forming, pressure forming, mold forming) of the film provided with the obtained hard coat layer was the same as that of the film of Example 3 in which the hard coat layer was not laminated. In addition, no crack occurred in the coat layer of the obtained molded article. Moreover, as a result of evaluating abrasion resistance, it was favorable that a scratch did not generate | occur | produce on the surface. On the other hand, when the scratch resistance of the molded article obtained by evaluating the moldability (vacuum forming, pressure forming, mold forming) of the forming film without forming the hard coat layer obtained in Example 3 was evaluated, a large number of scratches were generated. It was bad.

(Hard coat coating liquid)

The following materials were mixed in the mass ratio shown below, stirred for 30 minutes or more, and then undissolved matters and foreign substances were removed using a filter having a nominal filtration precision of 1 µm to prepare a coating solution A.

? Methyl ethyl ketone 48.50 mass%

6 Functional Polyurethane-Based Acrylic Monomer 35.00 Mass%

(Arakawa Chemical Industries, beam set 575)

2-functional polyurethane-based acrylic monomer 15.00 mass%

(Arakawa chemical industry, beam set 505-A6)

Photoinitiator 1.50 mass%

(Shiba, specialty made Irugacure 184)

The polyester film for molding of the present invention can be applied to a wide molding method because of its excellent moldability at the time of heat molding at low temperature and low pressure, and also when used in a room temperature atmosphere as a molded product, elasticity and shape It is excellent in stability (heat shrinkage characteristic, thickness nonuniformity), excellent solvent resistance, heat resistance, and small environmental load. Moreover, when unwinding the long film wound up in roll shape at the time of post-processing, since blocking and tearing hardly occur, productivity is excellent. In addition, since the smoothness and transparency are highly excellent, various printing and decorating methods such as convex printing, intaglio printing, flat printing, screen printing, offset printing, gravure printing, inkjet printing, flexographic printing, and the like in the printability improving layer of the film, and Three-dimensional molding of printing layers, pattern layers, etc. by decorating methods such as printing, transfer, painting, painting, vapor deposition, sputtering, CVD, and lamination, and then molding by various molding methods such as mold molding, pressure molding, and vacuum molding It is suitable for the decorating method and is excellent in in-mold moldability and emboss moldability. For this reason, it is suitable as a box or its member, such as a portable device such as a mobile phone, an audio, a portable player / recorder, an IC recorder, a car navigation system, a PDA, a notebook PC, a member for a name plate of a home appliance or an automobile, or a building material, The contribution to the industry is great.

Moreover, by containing a ultraviolet absorber in a film and reducing the transmittance | permeability of an ultraviolet region, light resistance can be provided and it is especially suitable as a shaping | molding material for the use (member for exterior or building materials of automobiles) used outdoors.

Claims (11)

As a polyester film for molding which consists of a biaxially-oriented polyester film containing a copolyester, (1) All the stress at 100% elongation in the longitudinal direction and the width direction of a film is 40-300 Mpa in 25 degreeC, and In 100 degreeC, the thermal contraction rate of 1-100 Mpa, the longitudinal direction and the width direction in 150 degreeC of (2) film is 0.01-5.0%, (3) haze is 0.1-3.0%, (4) the film of at least one surface. Surface roughness (Ra) of 0.005 ~ 0.030 ㎛, (5) surface orientation of 0.095 or less, (6) Co-polyester consists of (a) aromatic dicarboxylic acid component, ethylene glycol, and the glycol component which consists of a branched aliphatic glycol or alicyclic glycol as a copolymerization component, or (b) Copolyester consisting of an aromatic dicarboxylic acid component containing isophthalic acid as a terephthalic acid and a copolymerization component, and a glycol component containing ethylene glycol, (7) 5-50 mol% of content of the said copolymerization component in the said copolyester, (8) (A) It contains particle | grains in the said film, (B) It does not contain particle | grains in the said film, It contains particle | grains only in a surface layer, (9) Melting point of film is 200-245 degreeC Molding polyester film characterized by the above-mentioned. The method of claim 1, The biaxially-oriented polyester film contains a ultraviolet absorber, and the light transmittance in wavelength 370nm is 50% or less, The polyester film for shaping | molding characterized by the above-mentioned. The method of claim 1, The polyester film for shaping | molding polyester which comprises a biaxially-oriented polyester film further contains a 1, 3- propanediol unit or a 1, 4- butanediol unit as a glycol component. The method of claim 1, The polyester film for shaping | molding characterized by the surface layer mainly consisting of adhesive-modified resin and particle | grains. The polyester film for shaping | molding which provided the hard-coat layer in at least one surface of the polyester film for shaping | molding of any one of Claims 1-4. A polyester molded article formed by molding the polyester film for molding according to any one of claims 1 to 4 by any one of vacuum molding, pressure forming and mold molding. A polyester molded article provided with a hard coat layer on at least one side of the polyester molded article of claim 6. As a manufacturing method of the polyester film for shaping | molding which satisfy | fills the requirements of following (1)-(6) which become a biaxially-oriented polyester film containing a copolyester, In the heat setting treatment after biaxial stretching, the heat treatment is divided into two or more stages, The heat treatment temperature TS1 of the 1st stage is performed in the range of -5 degreeC--30 degreeC of the heat processing temperature TS2 of the 2nd stage, The second heat treatment temperature (TS2) is performed in the range of -5 ° C to -35 ° C of the melting point of the film, characterized in that the method for producing a polyester film for molding. (1) Co-polyester consists of (a) aromatic dicarboxylic acid component, ethylene glycol, and the glycol component which consists of a branched aliphatic glycol or alicyclic glycol as a copolymerization component, or (b) It consists of the aromatic dicarboxylic acid component containing isophthalic acid as a terephthalic acid and a copolymerization component, and the glycol component containing ethylene glycol. (2) 5-50 mol% of content of the said copolymerization component in the said copolyester, (3) (a) It contains particle | grains in the said film, or (b) The said film does not contain particle | grains, and contains particle | grains only in a surface layer. (4) The thermal contraction rate in the longitudinal direction and the width direction at 150 ° C. of the film is 0.01% to 5.0% (5) Haze is 0.1-3.0% (6) The surface roughness (Ra) of the film of at least one side is 0.005-0.030 micrometer The method of claim 8, And the second heat treatment temperature TS2 is the highest heat treatment temperature in the heat setting treatment. 10. The method according to claim 8 or 9, The molding polyester film further satisfies the following requirements (7) to (10). (7) The stress at the time of 100% elongation in the longitudinal direction and the width direction of a film is 40-100 Mpa in 25 degreeC, and 1-100 Mpa in 100 degreeC in all. (8) The branched aliphatic glycol is neopentyl glycol, and the alicyclic glycol is 1,4-cyclohexanedimethanol (9) Melting point of film is 200-245 degreeC (10) Surface orientation is less than 0.095 10. The method according to claim 8 or 9, The average particle diameter of the particle | grains contained in the said surface layer is 0.01-10 micrometers, and the particle content in the said surface layer is 0.01-25 mass%, The manufacturing method of the molding polyester film characterized by the above-mentioned.